CN101862642A - Preparation method and application of amphoteric chelate sorbent containing agricultural straw - Google Patents
Preparation method and application of amphoteric chelate sorbent containing agricultural straw Download PDFInfo
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- CN101862642A CN101862642A CN 201010207804 CN201010207804A CN101862642A CN 101862642 A CN101862642 A CN 101862642A CN 201010207804 CN201010207804 CN 201010207804 CN 201010207804 A CN201010207804 A CN 201010207804A CN 101862642 A CN101862642 A CN 101862642A
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Abstract
The invention relates to a preparation method and application of an amphoteric chelate sorbent containing agricultural straw. The sorbent is brownish-yellow solid powder, the nitrogen content is 10.83wt%, and the specific surface area is 12.93m<2>/g. The sorbent is prepared by taking agricultural straw, epoxy chloropropane and monochloroacetic acid as raw materials, taking trimethylamine or triethylamine as a grafting reaction agent and taking ethylenediamine, diethylenetriamine or triethylenetetramine as a cross-linking agent. The method of the invention has the advantages of simple production processes, economy, practicability, reproducibility and the like and can be suitable for large-scale production. The sorbent prepared by the invention has the characteristics of good stability, good adsorption effect, wide application range and the like, can be widely applied to treatment of waste water containing heavy metal ions, and has better treatment effect.
Description
Technical field
The present invention relates to a kind of method and application thereof that utilizes the agricultural stalk deep processing to prepare adsorbent, particularly a kind of preparation method of amphoteric chelate sorbent containing agricultural straw and application.
Background technology
According to United Nations Environment Programme (UNEP) statistics, the stalk that produced every year of the various crops of plantation is nearly 1,700,000,000 tons in the world, and it utilizes the purposes that roughly is divided three classes: the one, and the raw material of industry is mainly used in papermaking, accounts for 2.3% of total amount; The 2nd, animal feeding-stuff mainly is to make the plant-eating animal feed, accounts for 24.0% of total amount; The 3rd, directly burning or as biomass energy accounts for 31.5%, and all the other stalks are by idle waste or on-site incineration.
Mainly from departments such as plating, mining, smelting, chemical industry, unprocessed direct discharging will make water body be polluted to effluent containing heavy metal ions, the serious harm health, and to fishery, agricultural production generation harm.
At present, the external research that modifications such as some agricultural stalks such as bagasse, peanut shell, pomace, sawdust, cocoanut shell, banana skin, pine bark is prepared into ion adsorbent.But comprehensive domestic and international research present situation, utilize agricultural stalk to prepare adsorbent at present and be in the starting stage, and synthetic adsorbent only has simple function group mostly, can not satisfy the requirement that heavy metal yin, yang ion is removed simultaneously, has limited its utilization in the actual industrial wastewater treatment.Therefore, utilizing agricultural stalk development can remove the heavy metal anion, can remove the amphoteric chelate sorbent containing of heavy metal cation again, be of great significance and value, is the direction of environment-friendly material new technology application development from now on.
Prepare the report of amphion adsorbent about agricultural wastes, referring to: shaddock ped preparation of cellulose both sexes removal of heavy metal ions agent and the application in the electrolytic manganese wastewater treatment thereof, (2002) Fu Weichang, Wang Jihui, Dai Huimin; The preparation of both sexes bagasse cellulose and exchange Study on adsorption properties thereof, (2001) Zhu Jianglong, Zhang Mingjie, Chromate (Cr0
4 2-) and copper (Cu
2+) adsorption by dual-functional ion exchange resins made from agricultural by-products[J] .water research 40 (2006) 2541-2548. but these preparation methods or the secondary pollution problem that exists the alkali lye preliminary treatment to cause, or to problem such as the adsorption capacity of metal ion is lower.For preparing the amphoteric chelate sorbent containing of high adsorption capacity without alkali lye preliminary treatment agricultural stalk and be applied to the processing of effluent containing heavy metal ions, at present domesticly do not see bibliographical information.In the bibliographic data base, do not see the pertinent literature report at present abroad.
Summary of the invention
The adsorbent that the present invention is directed to the agricultural stalk preparation only has simple function group mostly, and the secondary pollution problem that the alkali lye preliminary treatment causes, or, provide a kind of preparation technology with amphoteric chelate sorbent containing agricultural straw that need not the pretreated high-adsorption-capacity of alkali lye of two kinds of functional groups of zwitterion to the deficiency of problem such as the adsorption capacity of metal ion is lower.
Amphoteric chelate sorbent containing agricultural straw of the present invention, its outward appearance are pale brown toner powder solid, and nitrogen content is 10.83wt%, and specific area is 12.93m
2/ g.
The general formula of amphoteric chelate sorbent containing is that example is expressed as with the cellulose:
The preparation method of amphoteric chelate sorbent containing of the present invention is:
(1) gets the agricultural stalk that particle diameter is 400～500 μ m, mix with 2～10 milliliters of epoxychloropropane according to every gram agricultural stalk, place there-necked flask to stir, in stirring, add 2～10 milliliters of N according to every gram agricultural stalk again, dinethylformamide is in 40～150 ℃ of following stirring reaction 30～150min;
(2) add crosslinking agent ethylenediamine, diethylenetriamine or triethylene tetramine in there-necked flask, mix according to the crosslinking agent of every gram agricultural stalk with 1～10 milliliter, continue stirring reaction 30～150min, reaction temperature is 40～150 ℃;
(3) the adding mass percentage concentration is 99% graft reaction agent triethylamine or trimethylamine solution, mixes stirring reaction 60～360min under 50～150 ℃ of conditions according to the graft reaction agent of every gram agricultural stalk with 2～10 milliliters;
(4) solid product that step (3) is obtained is used 0.1mol L successively
-1NaOH solution, 0.1mol L
-1HCl solution, concentration expressed in percentage by volume be 50% C
2H
5OH solution and washed with de-ionized water, under 60 ℃ of conditions, vacuum drying 8h～12h crosses sieve classification, obtains agricultural stalk anion adsorbent A;
(5) get A, in the there-necked flask of 250mL, mix with 13.45 milliliters of isopropyl alcohols and 0.67 ml distilled water according to every gram A, stir 10min down in 30 ℃, be that 40% NaOH mixes by every gram A with 0.5～1 milliliter of mass percentage concentration again, in 30 ℃ of following stirring reaction 30min; Mix with 0.25～3 gram chloroacetic acid by every gram A at last, in 20～80 ℃ of following stirring reaction 30～240min;
(6) the product washed with de-ionized water that step (5) is obtained until water outlet PH=7, at 60 ℃ of vacuum drying 8h～12h, is crossed sieve classification, obtains amphoteric chelate sorbent containing agricultural straw.
Described agricultural stalk is wheat straw waste, maize straw or rice straw, is preferably wheat straw waste.
Amphoteric chelate sorbent containing agricultural straw is applied in the effluent containing heavy metal ions processing as water treatment agent, application process is, at room temperature, regulate the pH value of waste water 4～6 with acid or alkali, the amphoteric chelate sorbent containing agricultural straw that adds 2g/L, stir 1～4h, isolate amphoteric chelate sorbent containing agricultural straw with filtration method then.
The amphoteric chelate sorbent containing that the present invention prepares is to be to be prepared under the raw material with agricultural stalk, epoxychloropropane, triethylamine (trimethylamine), ethylenediamine (diethylenetriamine or triethylene tetramine), isopropyl alcohol, chloroacetic acid.Have characteristics such as production technology is simple, economic, suitable, can be widely used in the improvement of pollutant effluents, and have water treatment effect preferably.
Description of drawings
Infrared spectrum (IR) contrast of the wheat straw amphoteric chelate sorbent containing of the former wheat straw waste of Fig. 1 and the embodiment of the invention 1.
Wherein, 3300-3500cm
-1Wide and the strong peak at place is in the wheat straw-the stretching vibration absworption peak of OH.The wheat straw amphoteric chelate sorbent containing is at 1338cm
-1There is strong absworption peak at the place, is the C-N stretching vibration, illustrates and has introduced amine groups in the wheat straw; At 1706-1720cm
-1The place is for more weak C=O carbonylic stretching vibration absworption peak, at 1611cm
-1Stronger C=O stretching vibration absworption peak has appearred in the place, illustrates and has introduced carboxylic group in the former wheat straw.
The specific embodiment
The present invention will be further described by the following examples, but be not limited thereto.
Embodiment 1:
(1) gets the wheat straw waste that particle diameter is 500 μ m, mix with 5 milliliters of epoxychloropropane, place there-necked flask to stir according to every gram agricultural stalk, in stirring, add 5 milliliters amount again according to every gram agricultural stalk, add N, dinethylformamide is in 100 ℃ of following stirring reaction 60min;
(2) add the crosslinking agent ethylenediamine in there-necked flask, mix according to the crosslinking agent of every gram agricultural stalk with 2 milliliters, continue stirring reaction 60min, reaction temperature is 100 ℃;
(3) the adding mass percentage concentration is 99% graft reaction agent triethylamine solution, mixes stirring reaction 180min under 100 ℃ of conditions according to the graft reaction agent of every gram agricultural stalk with 5 milliliters;
(4) solid product that step (3) is obtained is used 0.1mol L successively
-1NaOH solution, 0.1mol L
-1HCl solution, concentration expressed in percentage by volume be 50% C
2H
5OH and washed with de-ionized water, under 60 ℃ of conditions, vacuum drying 12h crosses sieve classification, obtains agricultural stalk anion adsorbent A;
(5) get A, in the there-necked flask of 250mL, mix with 13.45 milliliters of isopropyl alcohols and 0.67 ml distilled water according to every gram A, stir 10min down in 30 ℃, be that 40% NaOH mixes by every gram A and 0.75 milliliter of mass percentage concentration again, in 30 ℃ of following stirring reaction 30min; Mix with 0.51 gram chloroacetic acid by every gram A at last, in 60 ℃ of following stirring reaction 150min;
(6) the product washed with de-ionized water that step (5) is obtained until water outlet PH=7, at 60 ℃ of vacuum drying 12h, is crossed sieve classification, obtains amphoteric chelate sorbent containing agricultural straw.
Embodiment 2:
With wheat straw and epoxychloropropane stirring reaction, and adding crosslinking agent ethylenediamine, add triethylamine solution then, the charge ratio between them is a wheat straw: epoxychloropropane: ethylenediamine: triethylamine solution=1g: 2ml: 1ml: 5ml, prepare wheat straw anion adsorbent A; Then with A and isopropyl alcohol and water stirring reaction, and adding NaOH, add chloroacetic acid then, the charge ratio between them is A: (isopropyl alcohol+water): NaOH: chloroacetic acid=1g: (13.45ml+0.67ml): 0.75ml: 0.51g obtains the wheat straw amphoteric chelate sorbent containing.
Operating procedure is with embodiment 1, and difference is that the epoxychloropropane that adds is 2ml, and ethylenediamine is 1ml.
Embodiment 3:
With wheat straw and epoxychloropropane stirring reaction, and adding crosslinking agent ethylenediamine, add triethylamine solution then, the charge ratio between them is a wheat straw: epoxychloropropane: ethylenediamine: triethylamine solution=1g: 10ml: 10ml: 5ml, prepare wheat straw anion adsorbent A; Then with A and isopropyl alcohol and water stirring reaction, and adding NaOH, add chloroacetic acid then, the charge ratio between them is A: (isopropyl alcohol+water): NaOH: chloroacetic acid=1g: (13.45ml+0.67ml): 0.5ml: 0.51g obtains the wheat straw amphoteric chelate sorbent containing.
Operating procedure is with embodiment 1, and difference is that the epoxychloropropane that adds is 10ml, and ethylenediamine is 10ml, and the NaOH consumption is 0.5ml.
Embodiment 4:
With wheat straw and epoxychloropropane stirring reaction, and adding crosslinking agent diethylenetriamine, add triethylamine solution then, the charge ratio between them is a wheat straw: epoxychloropropane: diethylenetriamine: triethylamine solution=1g: 5ml: 2ml: 2ml, prepare wheat straw anion adsorbent A; Then with A and isopropyl alcohol and water stirring reaction, and adding NaOH, add chloroacetic acid then, the charge ratio between them is A: (isopropyl alcohol+water): NaOH: chloroacetic acid=1g: (13.45ml+0.67ml): 0.75ml: 0.5lg obtains the wheat straw amphoteric chelate sorbent containing.
Operating procedure is with embodiment 1, and difference is that used crosslinking agent is a diethylenetriamine, and the triethylamine consumption is 2ml, and the reaction temperature of (1), (2), (3) step is 50 ℃.
Embodiment 5:
With wheat straw and epoxychloropropane stirring reaction, and adding crosslinking agent triethylene tetramine, add trimethylamine solution then, the charge ratio between them is a wheat straw: epoxychloropropane: triethylene tetramine: trimethylamine solution=1g: 5ml: 2ml: 5ml, prepare wheat straw anion adsorbent A; Then with A and isopropyl alcohol and water stirring reaction, and adding NaOH, add chloroacetic acid then, the charge ratio between them is A: (isopropyl alcohol+water): NaOH: chloroacetic acid=1g: (13.45ml+0.67ml): 0.75ml: 0.51g obtains the wheat straw amphoteric chelate sorbent containing.
Operating procedure is with embodiment 1, and difference is that the crosslinking agent that adds is a triethylene tetramine, and the graft reaction agent is a trimethylamine.
Embodiment 6:
With wheat straw and epoxychloropropane stirring reaction, and adding crosslinking agent ethylenediamine, add trimethylamine solution then, the charge ratio between them is a wheat straw: epoxychloropropane: ethylenediamine: trimethylamine solution=1g: 5ml: 2ml: 5ml, prepare wheat straw anion adsorbent A; Then with A and isopropyl alcohol and water stirring reaction, and adding NaOH, add chloroacetic acid then, the charge ratio between them is A: (isopropyl alcohol+water): NaOH: chloroacetic acid=1g: (13.45ml+0.67ml): 0.75ml: 0.51g obtains the wheat straw amphoteric chelate sorbent containing.
Operating procedure is with embodiment 1, and difference is that the reaction time of (1), (2), (3) step is respectively 150min, 150min, and 360min, used graft reaction agent is a trimethylamine.
Embodiment 7:
With wheat straw and epoxychloropropane stirring reaction, and adding crosslinking agent ethylenediamine, add triethylamine solution then, the charge ratio between them is a wheat straw: epoxychloropropane: ethylenediamine: triethylamine solution=1g: 5ml: 2ml: 5ml, prepare wheat straw anion adsorbent A; Then with A and isopropyl alcohol and water stirring reaction, and adding NaOH, add chloroacetic acid then, the charge ratio between them is A: (isopropyl alcohol+water): NaOH: chloroacetic acid=1g: (13.45ml+0.67ml): 0.75ml: 0.51g obtains the wheat straw amphoteric chelate sorbent containing.
Operating procedure is with embodiment 1, and difference is that the reaction time of (5) step is respectively 10min, 30min, 240min.
Embodiment 8:
With wheat straw and epoxychloropropane stirring reaction, and adding crosslinking agent ethylenediamine, add triethylamine solution then, the charge ratio between them is a wheat straw: epoxychloropropane: ethylenediamine: triethylamine solution=1g: 5ml: 2ml: 5ml, prepare wheat straw anion adsorbent A; Then with A and isopropyl alcohol and water stirring reaction, and adding NaOH, add chloroacetic acid then, the charge ratio between them is A: (isopropyl alcohol+water): NaOH: chloroacetic acid=1g: (13.45ml+0.67ml): 0.75ml: 0.51g obtains the wheat straw amphoteric chelate sorbent containing.
Operating procedure is with embodiment 1, and difference is that the reaction temperature of (1), (2), (3) step is respectively 40 ℃, and 40 ℃, 50 ℃.
Embodiment 9:
With wheat straw and epoxychloropropane stirring reaction, and adding crosslinking agent ethylenediamine, add triethylamine solution then, the charge ratio between them is a wheat straw: epoxychloropropane: ethylenediamine: triethylamine solution=1g: 2ml: 2ml: 5ml, prepare wheat straw anion adsorbent A; Then with A and isopropyl alcohol and water stirring reaction, and adding NaOH, add chloroacetic acid then, the charge ratio between them is A: (isopropyl alcohol+water): NaOH: chloroacetic acid=1g: (13.45ml+0.67ml): 0.75ml: 0.25g obtains the wheat straw amphoteric chelate sorbent containing.
Operating procedure is with embodiment 1, and difference is that the epoxychloropropane that adds is 2ml, and the quality of chloroacetic acid is 0.25g.
Embodiment 10:
With wheat straw and epoxychloropropane stirring reaction, and adding crosslinking agent ethylenediamine, add triethylamine solution then, the charge ratio between them is a wheat straw: epoxychloropropane: ethylenediamine: triethylamine solution=1g: 5ml: 2ml: 5ml, prepare wheat straw anion adsorbent A; Then with A and isopropyl alcohol and water stirring reaction, and adding NaOH, add chloroacetic acid then, the charge ratio between them is A: (isopropyl alcohol+water): NaOH: chloroacetic acid=1g: (13.45ml+0.67ml): 0.75ml: 0.51g obtains the wheat straw amphoteric chelate sorbent containing.
Operating procedure is with embodiment 1, and difference is that used crosslinking agent is a diethylenetriamine, and the reaction temperature of (1), (2), (3) step is respectively 150 ℃, and 150 ℃, 150 ℃.
Embodiment 11:
With wheat straw and epoxychloropropane stirring reaction, and adding crosslinking agent ethylenediamine, add triethylamine solution then, the charge ratio between them is a wheat straw: epoxychloropropane: ethylenediamine: triethylamine solution=1g: 5ml: 2ml: 10ml, prepare wheat straw anion adsorbent A; Then with A and isopropyl alcohol and water stirring reaction, and adding NaOH, add chloroacetic acid then, the charge ratio between them is A: (isopropyl alcohol+water): NaOH: chloroacetic acid=1g: (13.45ml+0.67ml): 0.75ml: 0.51g obtains the wheat straw amphoteric chelate sorbent containing.
Operating procedure is with embodiment 1, and difference is that the triethylamine consumption is 10ml, and the reaction temperature of (1), (2), (3) step is respectively 150 ℃, and 40 ℃, 100 ℃.
Embodiment 12:
With wheat straw and epoxychloropropane stirring reaction, and adding crosslinking agent ethylenediamine, add trimethylamine solution then, the charge ratio between them is a wheat straw: epoxychloropropane: ethylenediamine: trimethylamine solution=1g: 5ml: 2ml: 5ml, prepare wheat straw anion adsorbent A; Then with A and isopropyl alcohol and water stirring reaction, and adding NaOH, add chloroacetic acid then, the charge ratio between them is A: (isopropyl alcohol+water): NaOH: chloroacetic acid=1g: (13.45ml+0.67ml): 0.75ml: 0.51g obtains the wheat straw amphoteric chelate sorbent containing.
Operating procedure is with embodiment 1, and difference is that used graft reaction agent is a trimethylamine, and the reaction temperature of (1), (2), (3) step is respectively 100 ℃, and 50 ℃, 100 ℃.
Embodiment 13:
With wheat straw and epoxychloropropane stirring reaction, and adding crosslinking agent ethylenediamine, add triethylamine solution then, the charge ratio between them is a wheat straw: epoxychloropropane: ethylenediamine: triethylamine solution=1g: 5ml: 2ml: 2ml, prepare wheat straw anion adsorbent A; Then with A and isopropyl alcohol and water stirring reaction, and adding NaOH, add chloroacetic acid then, the charge ratio between them is A: (isopropyl alcohol+water): NaOH: chloroacetic acid=1g: (13.45ml+0.67ml): 0.75ml: 0.51g obtains the wheat straw amphoteric chelate sorbent containing.
Operating procedure is with embodiment 1, and difference is that the triethylamine consumption is 2ml, and the reaction time of (1), (2), (3) step is respectively 30min, 30min, 60min.
Embodiment 14:
With wheat straw and epoxychloropropane stirring reaction, and adding crosslinking agent ethylenediamine, add triethylamine solution then, the charge ratio between them is a wheat straw: epoxychloropropane: ethylenediamine: triethylamine solution=1g: 2ml: 2ml: 5ml, prepare wheat straw anion adsorbent A; Then with A and isopropyl alcohol and water stirring reaction, and adding NaOH, add chloroacetic acid then, the charge ratio between them is A: (isopropyl alcohol+water): NaOH: chloroacetic acid=1g: (13.45ml+0.67ml): 0.75ml: 0.51g obtains the wheat straw amphoteric chelate sorbent containing.
Operating procedure is with embodiment 1, and difference is that the epoxychloropropane consumption is 2ml, and the reaction time of (1), (2), (3) step is respectively 150min, 150min, 360min.
Embodiment 15:
With wheat straw and epoxychloropropane stirring reaction, and adding crosslinking agent ethylenediamine, add triethylamine solution then, the charge ratio between them is a wheat straw: epoxychloropropane: ethylenediamine: triethylamine solution=1g: 5ml: 2ml: 5ml, prepare wheat straw anion adsorbent A; Then with A and isopropyl alcohol and water stirring reaction, and adding NaOH, add chloroacetic acid then, the charge ratio between them is A: (isopropyl alcohol+water): NaOH: chloroacetic acid=1g: (13.45ml+0.67ml): 0.5ml: 0.51g obtains the wheat straw amphoteric chelate sorbent containing.
Operating procedure is with embodiment 1, and difference is that used amount of sodium hydroxide is 0.5ml, and the reaction temperature of (5) step is respectively 30 ℃, and 30 ℃, 20 ℃.
Embodiment 16:
With wheat straw and epoxychloropropane stirring reaction, and adding crosslinking agent ethylenediamine, add triethylamine solution then, the charge ratio between them is a wheat straw: epoxychloropropane: ethylenediamine: triethylamine solution=1g: 5ml: 2ml: 5ml, prepare wheat straw anion adsorbent A; Then with A and isopropyl alcohol and water stirring reaction, and adding NaOH, add chloroacetic acid then, the charge ratio between them is A: (isopropyl alcohol+water): NaOH: chloroacetic acid=1g: (13.45ml+0.67ml): 0.75ml: 0.51g obtains the wheat straw amphoteric chelate sorbent containing.
Operating procedure is with embodiment 1, and difference is that used amount of sodium hydroxide is 0.75ml, and the reaction temperature of (5) step is respectively 30 ℃, and 30 ℃, 20 ℃.
Embodiment 17:
With wheat straw and epoxychloropropane stirring reaction, and adding crosslinking agent ethylenediamine, add triethylamine solution then, the charge ratio between them is a wheat straw: epoxychloropropane: ethylenediamine: triethylamine solution=1g: 5ml: 2ml: 5ml, prepare wheat straw anion adsorbent A; Then with A and isopropyl alcohol and water stirring reaction, and adding NaOH, add chloroacetic acid then, the charge ratio between them is A: (isopropyl alcohol+water): NaOH: chloroacetic acid=1g: (13.45ml+0.67ml): 0.75ml: 3g obtains the wheat straw amphoteric chelate sorbent containing.
Operating procedure is with embodiment 1, and difference is that the quality of chloroacetic acid is 3g, and the reaction time of (5) step is respectively 10min, 30min, 30min.
Embodiment 18:
With wheat straw and epoxychloropropane stirring reaction, and adding crosslinking agent ethylenediamine, add triethylamine solution then, the charge ratio between them is a wheat straw: epoxychloropropane: ethylenediamine: triethylamine solution=1g: 5ml: 2ml: 5ml, prepare wheat straw anion adsorbent A; Then with A and isopropyl alcohol and water stirring reaction, and adding NaOH, add chloroacetic acid then, the charge ratio between them is A: (isopropyl alcohol+water): NaOH: chloroacetic acid=1g: (13.45ml+0.67ml): 1ml: 0.51g obtains the wheat straw amphoteric chelate sorbent containing.
Operating procedure is with embodiment 1, and difference is that used amount of sodium hydroxide is 1ml, and the reaction time of (5) step is respectively 10min, 30min, 240min.
In embodiment 1-18, preferred embodiment 1 adsorbent.For confirm the wheat straw amphoteric chelate sorbent containing with synthetic effect and physicochemical property, embodiment 1 adsorbent is carried out performance characterization.The result is shown in Fig. 1 and table 1:
The physicochemical property of table 1 wheat straw amphoteric chelate sorbent containing and former wheat straw relatively
By above result as seen, the specific area of wheat straw amphoteric chelate sorbent containing is a bit larger tham former wheat straw, helps the carrying out of this adsorbent surface absorption to environmental pollutants.
The nitrogen element content of wheat straw amphoteric chelate sorbent containing increases to some extent, this is because in the modifying process of wheat straw waste, quaternary amines is introduced in stalk and triethylamine reaction, therefore wheat straw amphoteric chelate sorbent containing nitrogen element content is significantly improved, show that amine groups is introduced into, this is consistent with infrared result.
Embodiment 1 adsorbent is used to simulate the absorption of heavy metal ion Cr (VI) and Cu (II), simultaneously with former wheat straw, document in the amphion adsorbent reported the adsorption effect of Cr (VI) and Cu (II) is compared, the results are shown in table 2.
The different adsorbents of table 2 are to the maximal absorptive capacity q of Cr (VI) and Cu (II)
MaxRelatively
From above result as seen, no matter be to compare with former wheat straw, or compare with the amphoteric ion-exchange resin of reporting in the document, the wheat straw amphoteric chelate sorbent containing of the present invention preparation is all higher to the absorption property of Cr (VI) and Cu (II), shows that this adsorbent can be used as a kind of well behaved sorbing material and handles heavy metal zwitterion in the waste water.
Claims (4)
1. the amphoteric chelate sorbent containing of an agricultural stalk preparation is characterized in that outward appearance is pale brown toner powder solid, and nitrogen content is 10.83wt%, and specific area is 12.93m
2/ g; The general formula of amphoteric chelate sorbent containing is that example is expressed as with the cellulose:
2. the preparation method of the described amphoteric chelate sorbent containing agricultural straw of claim 1 is characterized in that, the preparation method is as follows:
(1) gets the agricultural stalk that particle diameter is 400～500 μ m, mix with 2～10 milliliters of epoxychloropropane according to every gram agricultural stalk, place there-necked flask to stir, in stirring, add 2～10 milliliters of N according to every gram agricultural stalk again, dinethylformamide is in 40～150 ℃ of following stirring reaction 30～150min;
(2) add crosslinking agent ethylenediamine, diethylenetriamine or triethylene tetramine in there-necked flask, mix according to the crosslinking agent of every gram agricultural stalk with 1～10 milliliter, continue stirring reaction 30～150min, reaction temperature is 40～150 ℃;
(3) the adding mass percentage concentration is 99% graft reaction agent triethylamine or trimethylamine solution, mixes stirring reaction 60～360min under 50～150 ℃ of conditions according to the graft reaction agent of every gram agricultural stalk with 2～10 milliliters;
(4) solid product that step (3) is obtained is used 0.1mol L successively
-1NaOH solution, 0.1mol L
-1HCl solution, concentration expressed in percentage by volume be 50% C
2H
5OH solution and washed with de-ionized water, under 60 ℃ of conditions, vacuum drying 8h～12h crosses sieve classification, obtains agricultural stalk anion adsorbent A;
(5) get A, in the there-necked flask of 250mL, mix with 13.45 milliliters of isopropyl alcohols and 0.67 ml distilled water according to every gram A, stir 10min down in 30 ℃, be that 40% NaOH mixes by every gram A with 0.5～1 milliliter of mass percentage concentration again, in 30 ℃ of following stirring reaction 30min; Mix with 0.25～3 gram chloroacetic acid by every gram A at last, in 20～80 ℃ of following stirring reaction 30～240min;
(6) the product washed with de-ionized water that step (5) is obtained until water outlet PH=7, at 60 ℃ of vacuum drying 8h～12h, is crossed sieve classification, obtains amphoteric chelate sorbent containing agricultural straw.
3. the preparation method of amphoteric chelate sorbent containing agricultural straw as claimed in claim 2 is characterized in that, described agricultural stalk is wheat straw waste, maize straw or rice straw.
4. the application of the described amphoteric chelate sorbent containing agricultural straw of claim 1, it is characterized in that, amphoteric chelate sorbent containing agricultural straw is applied in the effluent containing heavy metal ions processing as water treatment agent, application process is, at room temperature, the pH value of using acid or alkali adjusting waste water adds the amphoteric chelate sorbent containing agricultural straw of 2g/L 4～6, stir 1～4h, isolate amphoteric chelate sorbent containing agricultural straw with filtration method then.
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